Oil varnish



Patented Nov. 10, 1936 UNITED STATES PATENT OFFICE OIL VARNISH Wilhelm Breuers and Hermann Schatz, Ludwigshafen-on-the-Rhine, Germany, assignors to I. G. Farbenindu'strie Aktien'gesellschaft, Frankfort-on-the-Main, Germany N Drawing; Application February 9, 1934, Serial No. 710,526. In Germany February 16, 1933 18 Claims. (Cl. 134-17) The present invention relates to oil varnishes ings are obtained, which are neither extensible and a process of producing same. nor proof'against creasing. The softening points We have found that oil varnishes of excellent (determined according to the method of Kramerproperties can be obtained by incorporating with Sarnow) of the rubber isomerization products drying oils thermoplastic, resinous, brittle conyerusually lie betweenabout 50 and about 130 C. 5

sion products of rubber, being less unsaturated in most cases between 70 and 100 C. The visthan rubber, having a softening point between cosity of their solutions, as for example in oils, 50 and 130 0., preferably between 70 and is comparatively very small; 50 per cent solutions 100 C. and being readily soluble in aromatic, may therefore be worked up. The-color of the aliphatic open chain or cycloaliphatic' hydrocarrubber isomerization products is generally speak- 10 bons and in chlorinated hydrocarbons. ing yellowish to clear red-brown. The substances The rubber isomerization products to be emdissolve readily in aromatic, aliphatic open chain ployed according to this invention may be obor cycloaliphatic hydrocarbons, chlorinated hytained, for example, by causing isomerization drocarbons, as for example benzine, toluene, solagents to act on rubber or rubber solutions at vent naphtha, tetrahydronaphthalene, deca- 15 ordinary or elevated temperature and at atmoshydronaphthalene, benzine and petroleum fracpheric' or increased pressure, so that substances tions, such as'those distilling between 130 and of a pronounced resinous character are formed. 200 C., methylene chloride, carbon tetrahcloride Suitable isomerization agents are, for example, and chlorbenzene. They are not soluble, howsurface-active substances, such as the bleaching ever, in low alcohols and ketones. 20 earth known in the trade as Tonsil AC, which The preparation of the new, valuable oil varagents are advantageously allowed to act on nishes may be carried out in the usual manner by rubber, preferably in the presence of organic boiling with drying oils and subsequent addition solvents, at elevated temperatures, such as, for of siccatives, such as cobalt, lead or manganese example, between 200 and 300 C. The producnaphthanates. The boiling is carried out at tem- 25 tion of rubber isomerization products by the use peratures usually not above 350 (1., preferably at of such surface-active substances is disclosed in between about 240 and 260 C. For this purpose the co-pending application, Serial .No. 629,081, all drying oils and boiled drying oils are suitable, filed August 16, 1932, by one of us. Further such as linseed oil, linseed oil-stand oil, Chinaisomeri'zationagents which may also be employed wood oil and poppy-seed oil in any usual form.v 30 are. phosphorus oxychloride, sulfuric acid and The ratio of oil to resin component in the varorganic sulphonic acids. The isomerization prodnishes may be varied within wide limits, as for ucts have, like rubber, the composition (CsHsM example between 0.5:1 (preferably 2:1) and but are less unsaturated. varnishes prepared 20:1 (preferably 10:1). After boiling, suitable while employing rubber isomerization products solvents, such as mineral oil fractions, hydro- 35 which have been obtained in the presence of surcarbons of the benzine series,'ch10rinated hydroface-activesubstances frequently have especially carbons or any other solvent usually employed in favorable properties. the oil varnish industry, are added. The amount The products obtainable from thesaid resinous of the solvent varies within the widest limits- 40 substances by catalytic hydrogenation, which may according to the purposes for which the varnish 4 also be employed for the said purpose, are generis to be used. For examplevarnishes containing ally of lighter color than the non-hydrogenated 40 per cent of solvent may be prepared, but, of substances. As initial materials for the preparacourse, this percentage is only given by way of tion of isomerization products of the said kind, example and any other proportion of the combalata, gutta percha and like rubber-like subponents usual in the oil varnish industry may be 45 stances may be employed instead of rubber. The employed. varnishes may also be prepared by said hydrogenation products have, of course, a simply mixing a solution in benzine or other suitsomewhat higher content of hydrogen, for exable solvents of the isomerization products or ample, they contain from 8 to 8.8 atomic proporof their hydrogenation productswith stand oils tions, of hydrogen per 5 atomic proportions of and a siccative, and, if desired, pigments. 50 carbon. Other resins, either synthetic or natural, may

The conversion products of rubber to be used be employed together with the rubber isomerizaare characterized by the following properties. tion products. Pigments, softening agents and If solutions thereof in organic solvents are alother additions such as metal powders, may also lowed to evaporate on a substratum, brittle coatbe incorporated with the varnishes. 55

The application of the oil varnishes onto the substrata may be effected in any suitable manner. varnishes prepared in this way are distinguished, for example, by excellent adhesive power, high gloss and good rate of flow. An especially valuable property of the varnishes consists in the fact that they dry very rapidly. Even very fatty varnishes, as for example those con- ,taining 10 parts of oil to each part of resin, dry

considerably more rapidly when employing rubber isomerization products than correspondingly composed oil varnishes without these substances. The varnishes having the said additions also have excellent fastness to the influence of the atmosphere and the original high gloss remains unimpaired on exposure to light and rain. Furthermore, the corrosion-preventing action of the coatings prepared with the varnishes is excellent. For example sheet metal provided with clear coatings of varnishes of the said kind show no trace of rusting under the surface even after weathering for long periods in a strongly corrosive atmosphere.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are by weight.

Example 1 1 part of a resinous rubber isomerization product (obtained by heating crepe rubber in a rotary autoclave together with a bleaching earth known under the trade name Tonsil AC for five hours to 200 C., further five hours to 225 C. and finally for ten hours to from 250 C. to 260 C. and subsequently purifying the resultant product) is boiled for about an hour with 3 parts of a mixture of 9 parts of linseed oil-stand oil and 1 part of crude China-wood oil. The warm mixture is then incorporated with 0.5 per cent of a lead-cobalt naphthenate mixture (calculated with reference to the amount of oil). A clear varnish is obtained which, after dilution with 2.7 parts of .a benzine fraction boiling between 130 and 160 C., yields on sheet iron and wood coatings of excellent dispersion and very high gloss. The coatings are dust-dry after about 3 hours and are thoroughly dried throughout after about 30 hours. Manganese naphthenate may be used with a similar effect. Coatings produced with the said oil varnish are hard and possess a good gloss and coloration even after exposure to weathering for long times.

Example 2 1 part of the resinous rubber isomerization product according to Example 1 is boiled for from about 1 to 2 hours with 9 parts of the oil mixture mentioned therein and 0.5 per cent of a lead-cobalt naphthenate (calculated with reference to the amount of oil) is added to the still warm mixture. A varnish is obtained which is dried out when about 3 hours. It may be diluted with benzine.

If the coatings obtained with the said oilvarnish are exposed for long periods to weathering, they still have a satisfactory gloss and do not become yellow. The hardness of the coatings is good. Very valuable oil varnishes are obtained by adding pigments to varnishes produced in the manner described in the present and the preceding example. For example by the addition of carbon black, pigment deep black R (Schulz Julius, Farbstoiftabellen, 7th ed., vol. II, page 1'75) black varnishes and by the addition of zinc white, lithopone or titan white, white varnishes are obtained which have remarkable stability. Any other pigment, for example metal bronzes, may also be combined with the said oil varnishes. The said pigments are used in amounts usual in the oil-varnish industry.

What we claim is:

1. The process of producing oil-varnishes which comprises incorporating from 0.5 to 20 parts by weight of a drying oil with each part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having a softening point of between 50 and 130 C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation.

2. The process of producing oil-varnishes which comprises incorporating from 0.5 to 20 parts by weight of a drying oil with each part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having a softening'point of between and C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation.

3. The process of producing oil-varnishes which comprises incorporating from 2 to 10 parts by weight of a drying oil with each part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having a softening point of between 70 and 100 C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation.

4. The process of producing oil-varnishes which comprises incorporating from 0.5 to 20 parts by weight of a drying oil with each part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having a softening point of between 50 and C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, and heating the mixture to temperatures ranging up to 350 C.

5. The process of producing oil-varnishes which comprises incorporating from 0.5 to 20 parts by weight of a drying oil with each part by weight of 7 a thermoplastic, resinous, brittle conversion prod- C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, and heating the mixture to temperatures between about 240 and 260 C.

6. The process of producing oil-varnishes which comprises incorporating from 2 to 10 parts by weight of a dryingoil with each part byweight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having a softening point of between 70 and 100 0., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic.hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-activesubstances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, and heating the mixture to temperatures ranging up to 350 C.

'7. The process of producing oil-varnishes which comprises incorporating from 2 to 10 parts by weight of a drying oil with each part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having asQftening point of between 70 and 100 0., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated" hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, and heating the mixture to temperatures between about 240 and 260 C.

8. The process of producing oil-varnishes which comprises incorporating from 0.5 to 20 parts by weight of drying oil with each part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber,

having a-softening point of between 70 and 100 C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, and heating the mixture to temperatures between about 240 and 260 C. and adding an organic solvent.

9. The process of producing oil-varnishes which comprises incorporating from 2 to 10, parts by weight of a drying oil with each part by weight of a thermoplastic, resinous,- brittle conversion product of rubber being less unsaturated than rubber,

-' having a softening point of between 70 and 100 0., being readily soluble in aromatic, open chain and 260C. and adding benzine. r

10. The process of producing oil-varnishes which comprises incorporating from 2 to 10 parts by weight of a drying oil with each part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having a softening point of between 70 and 100 C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation and heating the mixture to temperatures between 240 and 260 C., adding an organic solvent and incorporating with the mass obtained a siccative.

11. The process of producing oil-varnishes which comprises incorporating from 0.5 to 20 parts by weight of a drying oil with a solution in an organic solvent of one part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber,

having a softening point of between 50 and 130 which comprises incorporating from 2 to 10 parts by weight of a drying oil with each part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having a softening point of between 70 and 100 C., being readily soluble in aromatic; open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, and heating the mixture to temperathan rubber, having a softening point of between 50 and 0., being readily soluble in aromatic, open chain aliphatic and .cycloaliphatic hydroselected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products'by catalytic hydrogenation.

14. Oil-varnishes comprising from 2 to 10 parts by weight of a drying oil and one part by weight of a thermoplastic, resinous, brittle conversion product of rubber being'less unsaturated than rubber, having a softening point of between and C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation;

15. Oil-varnishes comprising from 0.5 to 20 parts by weight of a drying oil, one part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber; having a softening point of between 70 and 100 C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of I surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, and an organic solvent.

16. Oil-varnishes comprising from 2 to 10 parts by weight of a drying oil, one part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber. having a softening point of between 70 and 100 C., being readily soluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons and chlorinated hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, an organic solvent and a siccative.

1'7. Oil-varnishes comprising from 2 to 10 parts by weight of a drying oil, one part by weight of a thermoplastic, resinous, brittle conversion product of rubber being less unsaturated than rubber, having a softening point of between 70 and 100 C., being readilysoluble in aromatic, open chain aliphatic and cycloaliphatic hydrocarbons, and being selected from the group consisting of the isomerization products obtained by reacting rubber with an isomerization agent of the class consisting of surface-active substances, phosphorus oxychloride, sulfuric acid and organic sulfonic acids and the products obtainable from such isomerization products by catalytic hydrogenation, an organic solvent, a siccative and a pigment.

18. Oil varnishes comprising from 0.5 to 20 parts by weight of a drying oil and one part by weight of a rubber conversion product obtainable by heating unvulcanized rubber in the presence of a finely divided, porous, surface active substance having a slightly acid reaction until a brittle product is obtained.

W'LLHELM BREUERS'. HLRMANN SCHATZ 

